2-benzylhex-5-en-1-ol | 1611477-04-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-benzylhex-5-en-1-ol
• CAS: 1611477-04-3
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: XNGYBMNFZKHUTG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  perfluorophenyl 2-benzylhex-5-enoate 在 samarium diiodide 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 2-benzylhex-5-en-1-ol 、 2-benzyl-5-methylcyclopentanol
  参考文献：
  名称：

  Ketyl-Type Radicals from Cyclic and Acyclic Esters are Stabilized by SmI₂(H₂O)_n: The Role of SmI₂(H₂O)_n in Post-Electron Transfer Steps

  摘要：

  Mechanistic details pertaining to the SmI2-H2O-mediated reduction and reductive coupling of 6-membered lactones, the first class of simple unactivated carboxylic acid derivatives that had long been thought to lie outside the reducing range of SmI2, have been elucidated. Our results provide new experimental evidence that water enables the productive electron transfer from Sm(II) by stabilization of the radical anion intermediate rather than by solely promoting the first electron transfer as originally proposed. Notably, these studies suggest that all reactions involving the generation of ketyl-type radicals with SmI2 occur under a unified mechanism based on the thermodynamic control of the second electron transfer step, thus providing a blueprint for the development of a broad range of novel chemoselective transformations via open-shell electron pathways.

  DOI：

  10.1021/ja503494b

文献信息

• On the Role of Pre- and Post-Electron-Transfer Steps in the SmI₂/Amine/H₂O-Mediated Reduction of Esters: New Mechanistic Insights and Kinetic Studies
  作者：Michal Szostak、Malcolm Spain、David J. Procter

  DOI：10.1002/chem.201400295

  日期：2014.4.7

  the reaction occurs via fast, reversible first electron transfer, and that the electron transfer from simple Sm(II) complexes to aliphatic esters is rapid. Notably, the mechanistic details presented herein indicate that complexation between SmI2, H2O and amines affords a new class of structurally diverse, thermodynamically powerful reductants for efficient electron transfer to carboxylic acid derivatives

  通过结合动力学、自由基时钟和反应性实验，研究了SmI 2介导的未活化酯还原的机制。动力学数据表明，所有反应组分（SmI 2、胺、H 2 O）都参与了速率方程，并且过渡态下布朗斯台德碱辅助的水去质子化促进了电子转移。使用经过验证的含环丙基自由基时钟表明，该反应通过快速、可逆的第一电子转移发生，并且从简单的 Sm(II) 配合物到脂肪族酯的电子转移是快速的。值得注意的是，本文提出的机理细节表明，SmI 2、H 2 O和胺之间的络合提供了一类结构多样、热力学强大的新型还原剂，可有效地将电子转移到羧酸衍生物，作为经典氢化物介导还原的有吸引力的替代品作为 C → C 键形成过程的酰基自由基等价物的来源。
• Ketyl-Type Radicals from Cyclic and Acyclic Esters are Stabilized by SmI₂(H₂O)_<i>n</i>: The Role of SmI₂(H₂O)_<i>n</i> in Post-Electron Transfer Steps
  作者：Michal Szostak、Malcolm Spain、David J. Procter

  DOI：10.1021/ja503494b

  日期：2014.6.11

  Mechanistic details pertaining to the SmI2-H2O-mediated reduction and reductive coupling of 6-membered lactones, the first class of simple unactivated carboxylic acid derivatives that had long been thought to lie outside the reducing range of SmI2, have been elucidated. Our results provide new experimental evidence that water enables the productive electron transfer from Sm(II) by stabilization of the radical anion intermediate rather than by solely promoting the first electron transfer as originally proposed. Notably, these studies suggest that all reactions involving the generation of ketyl-type radicals with SmI2 occur under a unified mechanism based on the thermodynamic control of the second electron transfer step, thus providing a blueprint for the development of a broad range of novel chemoselective transformations via open-shell electron pathways.